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Pulsed Laser Ablation
 Pulsed Laser Ablation
Advances and Applications in Nanoparticles
and Nanostructuring Thin Films

edited by
editors
Preben Maegaard Ion N. Mihailescu
Anna Krenz Anna Paola Caricato
Wolfgang Palz

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Pulsed Laser Ablation: Advances and Applications in

Nanoparticles and Nanostructuring Thin Films
Copyright © 2018 by Pan Stanford Publishing Pte. Ltd.
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 Contents

Preface xiii

1. Surface Energy and Nucleation Modes 1

Maura Cesaria
1.1 Introduction 2
1.2 Thermodynamic Background Concepts 5
1.2.1 Thermodynamic Potentials and Surface
Free Energy 5
1.2.2 Phase Transformations of a
Thermodynamic System and
Supersaturation 8
1.2.3 Strain and Epitaxial Growth 9
1.3 Thermodynamic Nucleation Theory and Growth
Modes 13
1.3.1 Principles of Nucleation Theory 14
1.3.2 Growth Modes at Thermodynamic
Equilibrium 20
1.4 Elementary Kinetic Processes on Surfaces and
the Energy Landscape 25
1.4.1 Adsorption, Real Substrates, and
Surface Elementary Processes 26
1.4.2 Characteristic Kinetic Coefficients,
Energy Barriers, and Timescales 30
1.5 Condensation Processes and Kinetic-Driven
Growth Modes 34
1.5.1 Kinetic Control of Nucleation 35
1.5.2 Intralayer and Interlayer Diffusion,
Island Coalescence, and Growth Modes 37
1.5.3 Microstructure Evolution 42
1.6 Deposition Techniques in Nanoscience and
Advantages of the Pulsed Laser Approaches 46
1.7 Growth Opportunities by the PLD Technique 50
1.7.1 Distinctive Characteristics of the PLD
Approach 51
vi Contents

1.7.2 Growth Manipulations by PLD 59

1.8 Conclusions 68

2. Nanosecond Laser Ablation and Processing of Solid

Targets in Vacuum or in a Low-Gas Atmosphere 85
Vincenzo Resta, Ramón J. Peláez, and
Anna Paola Caricato
2.1 Introduction 85
2.2 Plasma Dynamics and Expansion 86
2.2.1 Plasma Parameters: Temperature
and Density 91
2.2.2 Plasma Composition: Atom and Ion
Distribution/Yields 93
2.3 Production of Metal Nanoparticles by Pulsed
Laser Deposition 100
2.3.1 Dependence with the Number of
Laser Pulses in the Metal Target 101
2.3.2 Dependence with the Laser Fluence 106
2.3.3 Peculiarities of Pulsed Laser
Deposition in Nanoparticle Formation
and Dependence with the Substrate 110
2.4 Thermal Process 113
2.4.1 Substrate Temperatures 113
2.4.2 Postheating by Laser Irradiation 115

3. Nanosecond Laser Ablation of Solid Targets in a

High-Pressure Atmosphere 131
Sebastiano Trusso, Fortunato Neri, and
Paolo Maria Ossi
3.1 Introduction 132
3.2 Comparison between Some Basics of Laser
Ablation in Vacuum and in a Gas at High
Pressure 133
3.3 Nanoparticle Synthesis and Assembling
upon Ablation in a High-Pressure Gas:
Selected Examples 136
3.4 Deposition of Noble Metal Nanoparticle
Arrays for Application in Biomedical Sensing 142
3.5 Conclusions 150
 Contents vii

4. Femtosecond Laser Ablation of Solid Targets in

Vacuum and Low-Pressure Gas Atmosphere 155
Salvatore Amoruso
4.1 Introduction 156
4.2 Experimental and Theoretical Analyses of
the Early Stage of Femtosecond Laser Ablation 161
4.3 Experimental Analysis of Late Stages of
Femtosecond Laser Ablation and Plume
Propagation 167
4.3.1 High-Vacuum Expansion 168
4.3.2 Propagation in a Low-Pressure
Background Gas 174
4.4 Femtosecond Laser Ablation of Thin Films 179
4.5 Nanoparticles and Nanoparticle-Assembled
Films 180
4.6 Conclusions 182

5. Short-Pulse Laser Near-Field Ablation of Solid Targets

under Liquids 193
M. Ulmeanu, P. Petkov, F. Jipa, E. Brousseau, and
M. N. R. Ashfold
5.1 Introduction 193
5.2 Working Principle of the LILAC Lithography
Technique 195
5.2.1 Preparing the Si Substrates 196
5.2.2 Preparing the Colloidal Mask 197
5.2.3 Laser Processing Parameters 198
5.2.4 Focusing the Laser Beam through the
Liquids 198
5.2.5 Finite-Difference Time Domain
Simulations 200
5.3 Experimental Demonstrations 202
5.4 Conclusions 204

6. MAPLE Deposition of Nanomaterials 207

Enikö György and Anna Paola Caricato
6.1 Introduction 208
6.2 Ultraviolet Matrix-Assisted Pulsed Laser
Evaporation 215
viii Contents

6.3 Infrared Matrix-Assisted Pulsed Laser

Evaporation 230
6.4 Inverse Matrix-Assisted Pulsed Laser
Evaporation 234
6.5 Conclusions 236

7. Thin Films and Nanoparticles by Pulsed Laser

Deposition: Wetting, Adherence, and Nanostructuring 245
Carmen Ristoscu and Ion N. Mihailescu
7.1 Introduction 246
7.2 Wetting 248
7.2.1 Definitions 248
7.2.2 Case Examples 251
7.3 Adherence 254
7.3.1 Basic Mechanisms 254
7.3.2 Investigations and Examples 255
7.4 Nanostructuring 258
7.4.1 Definitions 258
7.4.2 Imaging of Nanostructures 259
7.4.2.1 Conventional imaging 259
7.4.2.2 Differential evanescent light
intensity imaging 260
7.4.3 Nanostructuring with Advanced PLD
Techniques 262
7.4.4 Applications 265
7.4.4.1 Metal oxides for gas sensing 265
7.4.4.2 Fuel cell elements 266
7.4.4.3 Nanoparticles for SERS 267
7.5 Conclusions 268

8. Core-Shell Nanoparticles for Energy Storage Applications 277

Manish Kothakonda, Briley Bourgeois, Brian C. Riggs,
Venkata Sreenivas Puli, Ravinder Elupula,
Muhammad Ejaz, Shiva Adireddy, Scott M. Grayson,
and Douglas B. Chrisey
8.1 Introduction 278
8.1.1 Nanoparticle Property Selection 280
8.1.2 Nanoparticle Synthesis 281
8.1.2.1 Core-shell nanoparticles
prepared by the grafting-from
route 281
 Contents ix

8.1.2.2 Core-shell nanoparticles

prepared by the grafting-to
route 283
8.2 Experimental Section 286
8.2.1 Nanoparticle Synthesis 286
8.2.2 Nanoparticles Synthesis by Pulsed
Laser Ablation 288
8.2.3 Synthesis of BaTiO3 Nanoparticles
by the Solvothermal Method 289
8.2.4 Polymerization of Nanoparticles 292
8.2.4.1 Synthesis of PGMA-BaTiO3
core-shell nanostructures
by grafting-from 292
8.2.4.2 Synthesis of PVDF-HFP-
GMA-BaTiO3 core-shell
nanostructures by grafting-to 294
8.3 Materials Characterization 295
8.4 Experimental Observation 296
8.4.1 Dielectric Properties and Leakage
Current Behavior 299
8.5 Conclusions 303

9. Nanoparticle Generation by Double-Pulse Laser

Ablation 317
Emanuel Axente, Tatiana E. Itina, and Jörg Hermann
9.1 Introduction 318
9.2 Typical Experimental Design for Laser–Matter
Interactions with Double Pulses 321
9.2.1 Collinear Double-Pulse Interaction
Geometry 322
9.2.2 Orthogonal Double-Pulse Interaction
Geometry 322
9.2.3 Experiment for NP Generation with
Delayed Short Laser Pulses 323
9.3 Investigation of Nanoparticles Produced by
Short Double-Pulse Laser Ablation of Metals 325
9.3.1 Correlation between Ablation
Efficiency and Nanoparticle Generation
in the Single-Pulse Regime 326
9.3.2 Influence of Interpulse Delay on
Plume Composition 327
x Contents

9.3.3 Influence of Interpulse Delay on

Ablation Depth and Crater Morphology 331
9.3.4 Overview of Other Investigations in the
Field of Double-Pulse Laser–Matter
Interactions 334
9.4 Modeling of Double-Pulse Laser Ablation 338
9.4.1 Fundamentals of Laser–Matter
Interactions 338
9.4.2 Numerical Simulations of Short
Double-Pulse Interaction with Materials 341
9.5 Conclusions and Perspectives 343

10. Ultrafast Laser-Induced Phenomena inside Transparent

Materials 357
Felix Sima, Jian Xu, and Koji Sugioka
10.1 Introduction 358
10.2 Characteristics of Glass Material Processing
by Ultrafast Laser Pulses 359
10.2.1 Interaction Mechanism of Ultrafast
Laser Pulses with Glasses 359
10.2.1.1 Nonlinear multiphoton
absorption 359
10.2.1.2 Heat accumulation effects 362
10.2.2 Spatial Resolution in Ultrafast Laser
Processing of Glass 363
10.3 Undeformative Processing: ULP-Induced
Internal Modifications 366
10.4 Subtractive Processing: Formation of 3D
Micro- and Nanofluidic Structure 370
10.4.1 Ultrafast Laser-Induced Modification
Followed by Selective Wet Etching 370
10.4.2 Liquid-Assisted ULP Processing 374
10.4.3 Pros and Cons of the ULP 3D
Subtractive Process 375
10.5 Additive Processing: ULP-Induced
Photopolymerization of Photoresists 376
10.5.1 Mechanisms and Limitations 376
10.5.2 Applications of Two-Photon
Polymerization 379
10.6 Hybrid ULP 3D Processing 381
 Contents xi

10.6.1 Combination of Subtractive and

Undeformative Processing 381
10.6.2 Combination of Subtractive and
Additive Processing 383
10.7 Challenges and Perspectives 385

11. Ultrafast Processes on Semiconductor Surfaces

Initiated by Temporally Shaped Femtosecond Laser
Pulses 399
P. A. Loukakos, G. D. Tsibidis, and E. Stratakis
11.1 Introduction 400
11.2 Experimental Details 402
11.3 Theoretical Details 403
11.4 Results and Discussion I: Si 403
11.5 Results and Discussion II: ZnO 416
11.6 Conclusions 420

12. Atomistic Simulations of the Generation of

Nanoparticles in Short-Pulse Laser Ablation of Metals:
Effect of Background Gas and Liquid Environments 425
Cheng-Yu Shih, Chengping Wu, Han Wu,
Maxim V. Shugaev, and Leonid V. Zhigilei
12.1 Introduction 426
12.2 Computational Setup for the Simulation of
Laser Interactions with Metals in a
Background Gas or Liquid Environment 429
12.2.1 Representation of Laser Interaction
with Metals 430
12.2.2 Representation of Background Gas
and Liquid Environments 433
12.3 Large-Scale MD Simulations of Laser Ablation
in Vacuum 435
12.4 Ablation in a Background Gas 442
12.5 Ablation in Liquids 445
12.6 Concluding Remarks 454

13. Laser Nanostructuring of Polymers 471

Esther Rebollar, Tiberio A. Ezquerra, and
Marta Castillejo
13.1 Introduction 472
xii Contents

13.2 LIPSS Formation Using Nanosecond Pulses 475

13.3 LIPSS Formation Using Femtosecond Pulses 478
13.4 Formation of LIPSS on Nonabsorbing Polymers 481
13.5 Formation of Alternative Periodic Structures 483
13.6 Applications of Polymer LIPSS 484
13.6.1 Polymer LIPSS for Cell Culture 484
13.6.2 Polymer LIPSS for SERS Substrates 485
13.6.3 Polymer LIPSS for Nonvolatile Organic
Memory Devices 486
13.7 Conclusions 488

14. Laser Materials Processing for Energy Storage

Applications 499
Heungsoo Kim, Peter Smyrek, Yijing Zheng,
Wilhelm Pfleging, and Alberto Piqué
14.1 Introduction 500
14.2 Background and Overview of Materials for
Energy Storage 501
14.3 Growth of Energy Storage Materials by
Pulsed Laser Deposition 503
14.3.1 PLD of Cathodes 505
14.3.2 PLD of Anodes 508
14.3.3 PLD of Solid-State Electrolytes 510
14.4 Printing of Energy Storage Materials by LIFT 512
14.4.1 LIFT of Ultracapacitors 514
14.4.2 LIFT of Li Ion Microbatteries 516
14.4.3 LIFT of Solid-State Electrolytes 520
14.5 3D Processing of Energy Storage Materials
by LS and LA 521
14.5.1 LA and LS of Thin-Film Electrodes 522
14.5.1.1 Laser annealing 523
14.5.1.2 LS of LCO thin films 524
14.5.1.3 LS of SnO2 thin films 526
14.5.1.4 LS of LMO thin films 527
14.5.2 LS of Thick-Film Electrodes 528
14.5.3 LS Turns Electrodes into Superwicking 530
14.6 Challenges and Future Directions 533
14.7 Summary 534

Index 545
 Contents xiii

Preface

Nanotechnology and nanomaterials are at the origin of major

progress, breakthroughs, and solutions to a vast number of
engineering, biology, and medicine challenges. In fact, at the
nanoscale, and at a macroscopic scale as well, the onset of size-
dependent phenomena occurs and matter begins to exhibit entirely
new properties. The advantage connected to the small feature size of
nanostructured materials is exploited in many different applications,
both in ordinary life and in high-technology fields.
Obviously, the possibility to valorize the new properties
of nanomaterials is strictly connected to the availability of
manufacturing processes and characterization techniques.
Among manufacturing methods, pulsed laser–based techniques
offer several advantages compared to “traditional” ones for the
fabrication of nanomaterials and surface nanostructures, due to
the possibility to tune many independent processing parameters.
Laser and laser ablation proved important and prospective in
various fields, spanning from a better understanding of fundamental
physical mechanisms and light–matter interactions to a large range
of applications in physics, chemistry, biology, medicine, materials
science, manufacturing technology, and even arts and conservation.
This book consists of 14 chapters covering a broad range of
topics, written by internationally recognized experts in the field,
on the recent advances in the application of laser ablation for the
generation of nanoparticles and surface nano- and microstructures
and their applications.
It includes a comprehensive overview of the classical theory
of growth, with a focus on the importance of kinetic factors and
processes in far-from-equilibrium deposition techniques such as
pulsed laser deposition (Chapter 1). The wetting, adherence, and
nanostructuring properties of the synthesized coatings, by pulsed
laser processes, are described and discussed in Chapter 7. A detailed
description of the mechanisms and significance of deposition
parameters on nanoparticle immobilization and production in
xiv Preface

different environments (e.g., vacuum, Chapter 2; a high-gas-pressure

atmosphere, Chapter 3; liquid, Chapter 5; and matrices, Chapter 6),
pulse duration (i.e., the ns regime, Chapters 2, 3, and 5; or the fs
regime, Chapters 4 and 5), and use of two time-delayed laser pulses
(Chapter 9) is provided. An overview of the results obtained in recent
molecular dynamic simulations of laser ablation of metal targets in
vacuum, a background gas, and a liquid environment (Chapter 12) is
also given.
The processing of materials by fs laser pulses has attracted
a great deal of attention because fs pulse energy can be precisely
and rapidly delivered to the material without detectable heat
perturbation of the neighboring zones. In some cases, periodic
micro- and nanostructures can be generated directly (without the
use of masks or chemical photoresists to relieve the environmental
concerns) in almost any samples from semiconductor to dielectric
materials and polymers, supplying relevant results to be used
in different applications like nanofluidics, nanophotonics, and
biomedical devices.
The effects of some key parameters, including multiple pulses,
variable pulse shaping, and fluence, which could be useful in the
laser nanostructuring of surfaces and micromachining of different
materials (e.g., dielectric, Chapter 10; semiconductor, Chapter 11; and
polymer, Chapter 13), are reviewed and discussed from fundamental
and/or applicative points of view. The use of laser-based material
processing techniques, such as pulsed laser deposition (PLD), laser-
induced forward transfer (LIFT), material processing via 3D laser
structuring (LS), and laser annealing (LA) techniques for energy
storage applications is analyzed in Chapter 14.
Next, Chapter 8 is devoted to the importance of the use of
core-shell nanoparticles when different material properties must
be merged at the nanoscale to meet the requirements for smart
applications.
In the opinion of the authors, the book offers a comprehensive
review of the latest advances in top research and development
in the laser material processing field for nanoparticles and
nanomicrostructure generation and exploitation of different kinds
of materials. Theoretical models are discussed by correlation with
advanced experimental protocols, to explain the fundamentals
and underline physical mechanisms of laser–matter interaction.
 Preface xv

The book was conceived as a starting point and guide for students
and young researchers who are beginning to initiate in the field of
nanostructures and nanoparticles.
Last but not least, the two editors would like to thank all of the
chapter contributors for their great efforts and kind cooperation in
preparing this book.
Ion N. Mihailescu and Anna Paola Caricato
2018
Chapter 1

Surface Energy and Nucleation Modes

Maura Cesaria
Department of Mathematics and Physics “Ennio De Giorgi,” University of Salento,
Via Arnesano, I-73100 Lecce, Italy
[email protected]

Deposition is a manufacturing process in which a precursor material

is delivered to a surface on which it reorganizes by interplay
between thermodynamics and kinetics. The evolution of the
microstructure of the deposit (layers with thicknesses between a
few atomic layers and several micrometers [films] or nanostructure
distributions or nanostructured films) is highly dependent on the
physical conditions (i.e., the deposition technique and parameters)
under which deposition takes place, apart from the choice of
materials. Understanding the mechanisms underlying the structural
and morphological evolution of a growing deposit is essential to
being able to tailor the properties and performances of functional
materials at the atomic scale depending on the deposition approach.
In this chapter a comprehensive overview to the classical theory
of growth will be given, with a focus on the importance of kinetic
factors and processes as well as the growth manipulations enabled

Pulsed Laser Ablation: Advances and Applications in Nanoparticles and Nanostructuring Thin Films
Edited by Ion N. Mihailescu and Anna Paola Caricato
Copyright © 2018 Pan Stanford Publishing Pte. Ltd.
ISBN 978-981-4774-23-9 (Hardcover), 978-1-315-18523-1 (eBook)
www.panstanford.com
2 Surface Energy and Nucleation Modes

by a prototypal far-from-equilibrium deposition technique, such as

pulsed laser deposition.

1.1 Introduction
The impossible-to-review large number of publications that deal
with growth arguments demonstrates a widespread interest at
both fundamental and technological levels in understanding the
parameters, processes, and kinetic mechanisms that determine
and tailor several growth regimes. This purpose has driven a great
amount of effort to either model growth theoretically for improving
the growth techniques or develop and optimize processing
approaches to drive growth far from thermodynamic equilibrium.
In regard to tailoring material functionalities and morphology, a
great deal of attention is being focused on nanostructures (systems
scaled down to dimensions below 100 nm along at least one spatial
direction) that lead to entirely new and challenging applicative
perspectives due to quantum confinement effects and a large
surface area–volume ratio. Since the fundamental properties of
nanoscaled systems are critically affected by size, shape, size and
shape dispersion, stoichiometry, and the surrounding environment,
the deposition approaches and process parameters play a key role in
driving growth and obtaining metastable phases as well as state-of-
the-art and tailorable morphology. To fabricate mesoscopic systems
two main types of processing approaches are applied, top-down
approaches (i.e., patterning performed in bulk material building
blocks by combining [photo, e-beam, or nanoimprint] lithography,
etching, and direct deposition on substrates) and bottom-up
approaches (i.e., structure assembling by self-assembly or self-
organization and selective growth from previously chemically or
physically synthesized nanoscale building blocks) [1–6].
To explain and predict the observed morphologies and their
evolution in growth experiments, equilibrium (thermodynamic)
models, which have been the primary stage of investigation
historically, may provide the starting information to be combined
with the out-of-equilibrium (kinetic) picture [7, 8]. Nucleation,
phase transformations, crystallization, and growth are examples of
processes requiring thermodynamic as well as kinetic treatment.
The kinetic framework is one of the most successful in describing
 Introduction 3

the nonequilibrium morphology of crystals in both bulk and

mesoscopic phases. Thermodynamics establishes whether a certain
transformation (chemical reaction or phase change) is allowed or
not on the basis of a decrease (leading to a global minimum) in
the free energy and gives an account of the forces driving such a
transformation [9–13]. From a thermodynamic standpoint, growth
is determined by the competition between surface and interface
free energy, as well as strain energy and strain relief. Such an
approach works if growth is driven close to equilibrium, that is,
under conditions not dominated by kinetic effects (how fast or slow
a process can occur [rate], adsorption, desorption, and diffusion).
Crystallization (i.e., the formation of crystals from the melt,
solution, or vapor phase) is a process very much concerned with
kinetics because the morphology evolution and shape of crystals are
highly influenced by kinetic factors and a complex energy landscape.
Indeed, in the thermodynamic picture, the species locally added on the
surface of any growing nanocrystal should migrate toward sites with
the lowest free energy. However, whenever surface diffusion is not
effective enough, a thermodynamically less favorable shape (leading
to a local rather than a global minimum of the free energy) may
result. All of this indicates that the final (nano)crystal morphology is
determined by the competition between kinetic factors, such as the
rates corresponding to deposition and surface diffusion. In general,
the deposition rate is determined by the rate at which the precursor
species are supplied and the diffusion rate is either a thermally or
kinetically activated process involving the motion of the deposited
species on a solid surface through hopping from site to site. Hence,
unbalance between the rates of deposition and surface diffusion by
well-controlled manipulation of the experimental parameters can
drive the growth toward equilibrium, close-to-equilibrium, or far-
from-equilibrium conditions.
Since in practice growth is a nonequilibrium process, competition
between thermodynamics and surface kinetics determines the final
morphology instead of a purely thermodynamics picture [14, 15].
Basic steps in the growth of materials by deposition are emission
of the species to be deposited from a source (heater for thermoionic
emission, high voltage for generating charged particle beams, pulsed
laser–irradiated target for inducing ablation), their transport from
the source to the system supporting the growing deposit (substrate)
4 Surface Energy and Nucleation Modes

nucleation, and growth by condensation processes of the deposited

species. The depositing species can diffuse under the drive of both
their self-energy and substrate thermal energy and then move to a
stable position on the substrate, where surrounding atoms may be
captured and incorporated, leading to the primary stage of growth,
that is, nucleation. Condensation develops through stages: formation
of clusters (i.e., groups of deposited species linked by a neighborhood
relation), nucleation (formation of stable clusters, termed “nuclei”),
dynamics of unstable and stable clusters, formation of an “island”
(growing nuclei) and its growth, island coalescence, percolation,
and structure development (amorphous, polycrystalline, single
crystalline, defects, roughness, and grain growth).
In this chapter these arguments will be discussed in detail in the
attempt to provide the basic information and knowledge to a reader
new to the growth subject and intending to gain physical insight into
mechanisms and processes involved in any deposition experiment. It
being impossible to review all the results reported in the literature,
discussion will aim at an overview of the field, draw guidelines to
establish a foundation for further specific readings, and treat the
underlying connections between deposition conditions and the
resulting structure and morphology with a focus on growth kinetics
driven by out-of-equilibrium approaches.
To start, a thermodynamic background will be given by dealing
with free energy, surface free energy, equilibrium criterion for a
crystal formation, strain, epitaxy, nucleation, growth modes, and
microstructure evolution under different conditions of temperature
and supersaturation. Then, deposition, condensation, and
morphological evolution will be discussed as related to the realistic
physical landscape, kinetic processes, and growth conditions. In
this respect, a brief mention of the deposition approaches used
for fabricating mesoscopic systems will be made to point out
both technological applications of the growth and possibilities for
exploiting the surface kinetics offered from growth driven far from
the thermodynamic equilibrium. Indeed, the energetic particle
beams used in nonthermal growth techniques, such as sputtering
and pulsed laser deposition (PLD), enable interaction mechanisms
between the substrate and the depositing beams, as well as growth
kinetics that are not enabled by near-equilibrium deposition
approaches, such as deposition from the gas/vapor phase [16–18].
 Thermodynamic Background Concepts 5

In particular, PLD will be discussed as a prototypical example of

the out-of-equilibrium deposition technique that allows growth
manipulations forbidden in the thermodynamic framework.

1.2 Thermodynamic Background Concepts

In this section basics of the classical thermodynamic approach
to nucleation theory and classification of growth modes (i.e., the
morphology taken on by a system grown close to thermodynamic
equilibrium) are introduced and discussed as related to the concepts
of free surface energy and strain.

1.2.1 Thermodynamic Potentials and Surface Free

Energy
In thermodynamics, two basic thermodynamic potential functions
are usually introduced to describe a system: the Gibbs free energy
G = H – TS and the Helmholtz free energy F = U – TS, where U is
the internal energy, T is the absolute temperature, H is the enthalpy,
and S is the entropy of the system [19–21]. For a multicomponent
system of N entities, the internal energy is given by U = TS – PV – Σiμi,
where P and V are the macroscopic variables pressure and volume,
respectively, and μi is the chemical potential of the component i (i =
1, . . . , N) of the system [19–21].
The possibility of any transformation (such as phase change,
nucleation, condensation, or chemical reaction) depends on the
sign of the change ΔG of the Gibbs free energy: a transformation
is classified as thermodynamically forbidden if ΔG > 0, allowed if
ΔG < 0, and in equilibrium if ΔG = 0. A system in thermodynamic
nonequilibrium evolves in such a way so as to reach equilibrium
through some driving forces, resulting in mass or energy transport.
As a thermodynamic criterion to determine operatively the
thermodynamically stable phase of a system, for given temperature
and pressure (or volume), the system will evolve spontaneously in
order to minimize the Gibbs and Helmholtz free energies under the
appropriate boundary conditions or to increase entropy at constant
energy, volume, and particle numbers in the system [21, 22].
6 Surface Energy and Nucleation Modes

Investigation of the conditions under which structure formation

and phase formation/transition processes may proceed is one main
focus in thermodynamics. General physical principles leading to the
equilibrium form of a crystal were first systematically formulated
by J. W. Gibbs on the basis of the total free energy G expressed as the
sum of the free energies of the volume, the surface, and the edges
and corners of the crystal [23]. It was pointed out that in the case of
a nanometer-size crystal, the influence of edges and corners cannot
be neglected. For a given volume, the minimization of the surface
energy of the crystal was identified as the criterion determining its
equilibrium form.
Basically, the surface free energy is defined as the work required
to build a surface of a unit area in contact with vacuum at constant
temperature, volume, and chemical potential. Microscopically, it
originates from surface bonds that are weaker than the correspond-
ing bulk bonds due to a reduced degree of coordination with their
neighbors, resulting in lower cohesive energy of the crystal. The
main contribution to the enthalpy term of the free energy stems
from the chemical bonding, and the stronger the bonds, the smaller
the interfacial free energy. Since the difference in the interatomic en-
ergy between bulk atoms and surface atoms is the origin of surface
energy, altering surface atomic arrangements (e.g., by deposition,
diffusion and growth) or straining a surface can change its surface
energy.
The surface free energy determined from microscopic
interactions (bonds) at an interface (heterogeneous boundary)
is termed “interface energy” or “interfacial free energy.” Since at
a given volume the minimum surface area leads to the minimum
of thermodynamic potential, low-energy faces are preferentially
expressed.
The total free energy of a system with a surface of area A (e.g., an
interface) is given by G = Gbulk + γA, where Gbulk is the free energy of
the bulk and γ is the surface energy (i.e., the excess free energy due
to broken bonds close to the surface). An increase in the free energy
of the system (ΔG) due to an increase in the surface area ΔA can be
expressed as ΔG = γ ΔA under the assumption that γ does not depend
on the area A. On the basis of this formalism, mathematically, the
 Thermodynamic Background Concepts 7

Gibbs condition (minimization of the surface energy of the crystal)

demands that, at a fixed volume, the total surface free energy of the
crystal ΣiγiAi is a global minimum, where γi and Ai are the surface free
energy and area, respectively, of the face ith of the crystal and the
summation is taken over all the faces of the crystal [10, 12, 24, 25].
According to the Gibbs criterion, a crystal forms by assuming
a shape of minimal surface energy for a given volume. In isotropic
systems, where the surface free energy does not depend on the
direction, a spherical shape minimizes the total surface area at a fixed
volume. In anisotropic systems the surface free energies depend on
the crystallographic planes identified by the Miller indices klm (γi =
γklm,i). Usually the densest planes of crystals grow the fastest because
of the higher potential energy decrease resulting from incorporation
of surface diffusing species due to the higher density of bonding
sites.
Since the surface free energy reflects the cost in energy
when bonds are broken, if only interactions between the nearest
neighbors are considered and the crystal is surrounded by vacuum
(broken bond approximation), then the specific surface free energy
of a crystallographic plane can be calculated by γklm = (1/2)NBερA,
where NB is the number of broken bonds per surface unit cell (or per
surface atom), ε is the bond strength, and ρA is the number of surface
atoms per unit area [26]. The prefactor 1/2 accounts for the fact that
each bond involves two atoms. More accurate calculations of the
surface free energies require the inclusion of interactions with the
second- and third-nearest neighbors, surface relaxation, and surface
adsorption of chemical species ([27] and references therein). By
combining crystal anisotropy and free-energy minimization, one may
come up with faceted crystal shapes. In fact, while isotropic interface
free energy induces a sphere as the equilibrium shape, for anisotropic
(i.e., depending on orientations) interface free energy the Wulff
construction can be used [28–30] for determining the equilibrium
shape of a crystal in vacuum geometrically by a polar plot of surface
energies. According to the Gibbs–Wulff theorem, at equilibrium the
distances of the borders from the crystal center are proportional to
their surface free energy, that is, γklm,i /hi = constant, where γklm,i and
hi are the specific surface free energy as a function of the orientation
8 Surface Energy and Nucleation Modes

and the distance to the center for the ith facet, respectively. It results
in an average interface free energy corresponding to a hypothetical
spherical cluster having the same volume and the same interface
energy as the real one with a faceted shape (closed polyhedron)
rather than a spherical equilibrium shape. Therefore, when the
growth of a single crystal occurs in vacuum under thermodynamic
control, a closed enlarging polyhedron is expected according to the
Wulff theorem.
However, since the equilibrium shape of a crystal is determined
by the interplay among surface free energies associated with
different crystallographic facets, modified ratios between such
energies may involve shapes other than the ones predicted by the
Wulff theorem. This evidence points to the role played by kinetic
versus thermodynamic control. In addition, the surface free energy
can act to destabilize the crystal for increasing the surface-to-volume
ratio (i.e., decreasing crystal size), which makes surface energy a
key quantity in driving morphology and mechanical and thermal
stability of nanosystems.

1.2.2 Phase Transformations of a Thermodynamic

System and Supersaturation
Another important argument in thermodynamics deals with phase
transformations of a thermodynamic system. The occurrence of any
transformation from the vapor phase to a condensed phase (liquid
or solid) demands a partial pressure (PV) exceeding the equilibrium
vapor pressure with respect to its condensed phase (PV,e) at the local
temperature T. Notably, the vapor pressure over a curved surface is
greater than that over the corresponding flat surface, as described
by the so-called Kelvin–Gibbs relation.
The thermodynamically stable phase corresponds to the
minimum of G, and transitions of the system correspond to a change
in the Gibbs free energy, given as difference between the values of G
in the starting and final states, that represents the driving force of the
transformation. Any vapor-to-solid transition of a thermodynamic
system (e.g., nucleation and condensation) can be described by
a change in the Gibbs free energy ΔG = ΔGV + ΔGS, where ΔGV and
 Thermodynamic Background Concepts 9

ΔGS refer to the volume and surface contribution to ΔG, respectively.

Usually, the energy release accompanying the transition is expressed
not in terms of total free-energy change but rather as the change
in chemical potential Δμ given as the difference of the chemical
potentials associated with the initial and final phases (i.e., Δμ =
μinitial – μfinal). The larger the Δμ, the greater is the driving force for
crystallization [31]. For the description of phase formation in solids,
Δμ is also a convenient measure of the so-called supersaturation
ratio SS expressed by (1 + SS) = P/Pe, where Pe is the equilibrium
vapor pressure of the infinitely extended condensed phase and P is
the actual value of the partial pressure. Therefore, the relationship
between Δμ and SS is given by the formula Δμ = kBT ln(1 + SS).
The supersaturation is a critical parameter in condensation
processes [32]. The situations associated with P = Pe, P < Pe, and P >
Pe are termed “saturated,” “undersaturated,” and “supersaturated,”
respectively. Supersaturated conditions, corresponding to Δμ >
0 (namely, ΔGV < 0), are a prerequisite to initiate condensation
processes as well as to make possible nucleation and subsequent
growth.

1.2.3 Strain and Epitaxial Growth

Crystals may form from liquid (precipitation from an aqueous
solution), melt (solidification), gas/vapor (deposition), and another
crystal (transformation, replacement, or metamorphism). In any
case, the minimization of the free energy is not an absolute criterion
for the formation of a crystal because minimization of the strain
energy also plays a role [33].
Strain or stress is commonly introduced by the growth of
heterostructures, namely systems consisting of different materials, as
a result of deposition or growth (growth stress), defects, constraints
imposed by mismatch in the thermal expansion coefficients
(playing during high-temperature growth or postdeposition
annealing), and/or structural misfit. Hence, three main classes of
stress can be identified: intrinsic or growth stress (developing due
to either defects in the deposit or the choice of growth approach
and conditions), thermal stress (caused by differential thermal
expansion), and misfit strain (arising from lattice misfit). Internal
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